CN108946751B - Preparation method and application of boron hexa-oxygen - Google Patents
Preparation method and application of boron hexa-oxygen Download PDFInfo
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Abstract
The invention discloses a preparation method and application of boron hexaoxide. The invention is provided withBoron powder is used as raw material, and boron hexaoxide, namely B, is synthesized at low temperature by oxidizing crystal boron and utilizing the oxidation exothermic reaction of the crystal boron6And O. The preparation method provided by the invention has the advantages of low cost, low energy consumption and simple synthesis process, the obtained boron hexaoxide has strong visible light absorption, is applied to photocatalytic water splitting for hydrogen production and photocatalytic reduction of carbon dioxide for the first time, shows high stability and good visible light catalytic activity, and is a non-metal photocatalyst, so that the boron hexaoxide has high scientific significance and application value in the field of new energy development.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a preparation method and application of boron hexaoxide.
Background
The boron hexaoxide belongs to a light element alpha rhombus boron-rich compound, has light weight, super hardness, high melting point, high strength, high elastic modulus and excellent high-temperature thermoelectric property, and is particularly suitable for being applied to extreme operating environments such as mining, petrochemical industry, weapon armor and nuclear industry. The traditional production of boron hexaoxide is synthesized by mixing boron powder and boron trioxide and roasting at high temperature of 1200-1800 ℃ under the protection of inert atmosphere, and has the problems of high cost, high energy consumption and the like. Therefore, the synthesis method which is low in cost, low in energy consumption and simple in preparation method is developed, and has important scientific significance and application value.
The technology of photocatalytic water splitting hydrogen production and photocatalytic carbon dioxide reduction is one of effective methods for solving the problems of current energy and environment, and is a research hotspot in the field of new energy at present. The raw materials for preparing hydrogen by photocatalytic water decomposition are light and water, which are inexhaustible resources in a certain sense, and the hydrogen obtained from the water is used as an energy source to generate water (H)2+O2＝H2O), is a completely sustainable development and utilization, and hydrogen is more a clean energy source with high combustion value, high efficiency. The photocatalytic reduction technology of carbon dioxide is an environment-friendly technology for recycling and reusing carbon dioxide which is newly developed. The technology simulates photosynthesis of green plants, and utilizes sunlight and a photocatalyst to convert carbon dioxide and water into carbon monoxide or hydrocarbon fuel. The technology of photocatalytic water splitting hydrogen production and carbon dioxide reduction has attracted wide attention at home and abroad. Most of the traditional photocatalysts generally contain transition metals and even noble metals, and the photoresponse of part of the photocatalysts is mainly in an ultraviolet light area, has no response to visible light, is poor in stability and easy to activate, and is not beneficial to large-scale application. Thus looking for novel visible light responsesThe non-metal photocatalyst material has important scientific significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of boron hexaoxide, which have the advantages of low cost, low energy consumption and simple process flow.
The technical scheme of the invention is as follows:
a process for preparing boron hexaoxide (B) from boron powder by oxidizing crystal boron and oxidizing the heat generated by its oxidizing reaction at ordinary temp and pressure6O, specifically comprising the following steps:
(1) amorphous boron powder or boron powder with crystallinity is taken as a raw material, when the amorphous boron powder is adopted, the amorphous boron powder is firstly placed in a tube furnace, and is roasted for 120-600 min at 900-1300 ℃ in an argon atmosphere, so as to be converted into the boron powder with crystallinity;
(2) adding boron powder with crystallinity into an oxidizing inorganic acid solution, ultrasonically dispersing for 0-30 min at 5-40 ℃ by using an ultrasonic instrument, and reacting for 30-240 min in an oil bath at 25-100 ℃;
(3) and (3) diluting the solution obtained in the step (2), performing centrifugal separation, respectively cleaning with deionized water and ethanol, and then drying the obtained powder at 50-80 ℃ for 4-8 h to obtain the boron hexaoxide.
Further, in the step (1), the argon atmosphere is high-purity argon with the purity of more than 99%, the flow rate is 30-100 mL/min, one bubble per second is kept to be the best, the temperature is programmed, and the temperature rise rate is 2-10 ℃/min.
Further, in the step (2), the oxidizing inorganic acid is one or more than two of nitric acid, sulfuric acid or hydrogen peroxide; the mass fraction of the oxidizing inorganic acid solution is 30-70%; the dosage of the oxidizing inorganic acid solution is 50-100 ml/(0.5-2) g of boron powder, namely 0.5-2 g of boron powder is added into 50-100 ml of the oxidizing inorganic acid solution.
The application of the boron hexaoxide prepared by the method in the photocatalytic decomposition of water to prepare hydrogen comprises the following steps:
adding boron hexa-oxygen into a photocatalytic reaction system, and then adding 10-200 mg: adding 50-120 mL of aqueous solution of alcohol with volume fraction of 0-50% as a solvent, putting in magnetons, vacuumizing a photocatalytic reaction system by a vacuum pump, carrying out a photocatalytic water hydrogen decomposition experiment by using a xenon lamp as a light source under magnetic stirring, carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system at the same reaction interval, and carrying out quantitative analysis by using gas chromatography to determine the content of a product.
Further, the alcohol aqueous solution is one or two of methanol and ethanol.
Further, the xenon lamp is provided with a 400 nm cut-off filter, and the light source is visible light.
The application of the boron hexaoxide prepared by the method in photocatalytic reduction of carbon dioxide is characterized by comprising the following steps:
adding boron hexa-oxygen into a photocatalytic reaction system, and then adding 10-200 mg: adding 1-3 mL of deionized water, replacing air in the photocatalytic reaction system with carbon dioxide gas for 2-5 times, introducing carbon dioxide to normal pressure, carrying out a photocatalytic reduction carbon dioxide experiment by using a xenon lamp as a light source, carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system at the same reaction interval, and carrying out quantitative analysis by using gas chromatography to determine the content of the product.
The invention has the beneficial effects that:
(1) the invention provides a brand-new preparation method of boron hexa-oxygen. Compared with the prior art, the preparation method has the advantages of simple process, mild reaction conditions and low energy consumption, and the purity of the prepared boron hexaoxide is high and reaches more than 99%.
(2) The boron hexaoxide prepared by the method has higher specific surface area, so that the boron hexaoxide has more active sites and is more beneficial to catalytic reaction.
(3) The boron hexaoxide prepared by the method is applied to the field of photocatalytic solar energy conversion for the first time.
(4) The boron hexaoxide prepared by the invention has stronger visible light absorption, is applied to photocatalytic water decomposition hydrogen production and photocatalytic reduction of carbon dioxide for the first time, shows high stability and better visible light catalytic activity, is a non-metal photocatalyst, and thus has higher scientific significance and application value in the field of new energy development.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of boron hexaoxide produced using hydrogen peroxide in example 1.
FIG. 2 is an X-ray diffraction (XRD) pattern of boron hexaoxide from nitric acid in example 2.
FIG. 3 is a graph showing the performance of photocatalytic hydrogen production by water decomposition under the conditions of example 5 for boron hexaoxide prepared in example 1.
FIG. 4 is a graph showing the performance of boron hexaoxide prepared in example 1 in the photocatalytic reduction of carbon dioxide under the conditions of example 6.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Preparation of boron hexa-oxygen
(1) Placing amorphous boron powder in a tube furnace, roasting at 1200 ℃ for 600min under the argon atmosphere, and converting into boron powder with certain crystallinity;
(2) adding 1g of boron powder with crystallinity obtained in the step (1) into 100mL of 30 wt% hydrogen peroxide solution, ultrasonically dispersing for 20min by using an ultrasonic instrument at the temperature of 20 ℃, and then reacting for 60min at the temperature of 60 ℃;
(3) after the reaction in the step (2) is finished, performing centrifugal separation, respectively cleaning the powder with deionized water and ethanol for three times, and drying the powder in an oven at 60 ℃ for 6 hours; obtaining boron hexa-oxygen.
Through testing, as shown in figure 1, the X-ray diffraction pattern shows that the purity of the boron hexaoxygen is more than 98 percent.
Example 2
Preparation of boron hexa-oxygen
(1) Placing amorphous boron powder in a tube furnace, calcining for 120min at 1000 ℃ under the argon atmosphere, and converting into boron powder with certain crystallinity;
(2) slowly adding 1g of boron powder with crystallinity obtained in the step (1) into 100ml of 60 wt% concentrated nitric acid solution, and then reacting for 60min at 70 ℃;
(3) diluting the solution after the reaction in the step (2), performing centrifugal separation, respectively washing with deionized water and ethanol for three times, and drying the obtained powder in an oven at 80 ℃ for 6 hours; obtaining boron hexa-oxygen.
Through testing, as shown in figure 2, the X-ray diffraction pattern shows that the purity of the boron hexaoxide is more than 98 percent.
Example 3
Preparation of boron hexa-oxygen
(1) The raw material boron powder adopts boron powder with crystallinity. Adding 1g of boron powder with crystallinity into 100mL of 30 wt% hydrogen peroxide solution, ultrasonically dispersing for 10min at 20 ℃ by using an ultrasonic instrument, and then reacting for 240min at 100 ℃;
(2) diluting the solution after the reaction in the step (1), performing centrifugal separation, respectively washing with deionized water and ethanol for three times, and drying the obtained powder in an oven at 50 ℃ for 6 hours; obtaining boron hexa-oxygen.
The purity of the boron hexaoxide is more than 99 percent through tests.
Example 4
Preparation of boron hexa-oxygen
(1) The raw material boron powder adopts boron powder with crystallinity. Adding 1g of boron powder with crystallinity into 100mL of 60 wt% nitric acid solution, ultrasonically dispersing for 10min at 5 ℃ by using an ultrasonic instrument, and then reacting for 180min at 90 ℃;
(2) diluting the solution after the reaction in the step (1), performing centrifugal separation, respectively washing with deionized water and ethanol for three times, and drying the obtained powder in an oven at 50 ℃ for 6 hours; obtaining boron hexa-oxygen.
The purity of the boron hexaoxide is more than 99 percent through tests.
Example 5
Hydrogen test for photocatalytic decomposition of boron hexaoxide
Weighing 50mg of photocatalyst, dispersing the photocatalyst in 100mL of ethanol aqueous solution with volume fraction of 20%, taking ethanol in the solution as a photocatalytic sacrificial agent, putting magnetons into the solution, vacuumizing a photocatalytic reaction system by a vacuum pump, performing a photocatalytic hydrogen decomposition experiment by taking a 300W xenon lamp as a light source under magnetic stirring, wherein the reaction intervals are the sameAnd (3) carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system, and carrying out quantitative analysis by using gas chromatography to determine the content of the product. And recovering the catalyst after the reaction is finished. FIG. 3 is a graph showing the performance of boron hexaoxide photocatalytic water splitting to produce hydrogen gas obtained in example 1. As can be seen from the figure, the catalytic effect of the boron hexaoxide is not reduced after 4 rounds of tests, which indicates that the prepared boron hexaoxide has stable photocatalytic effect and the hydrogen production rate under visible light reaches 5.48 mu mol g-1·h-1。
Example 6
Photocatalytic reduction carbon dioxide testing of boron hexa-oxide
Weighing 10mg of photocatalyst, adding 2mL of deionized water, replacing air in the photocatalytic reaction system with carbon dioxide gas for 2-5 times, introducing carbon dioxide to normal pressure, carrying out a photocatalytic reduction carbon dioxide experiment by using a xenon lamp as a light source, carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system at the same reaction interval, and carrying out quantitative analysis by using gas chromatography to determine the content of a product. FIG. 4 is a graph showing the results of measuring the performance of carbon monoxide prepared by photocatalytic reduction of carbon dioxide with boron hexaoxide obtained in example 1, wherein the production rate of carbon monoxide is 1.82. mu. mol. g-1·h-1。
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the boron hexaoxide is characterized by comprising the following steps:
(1) amorphous boron powder or boron powder with crystallinity is taken as a raw material, when the amorphous boron powder is adopted, the amorphous boron powder is firstly placed in a tube furnace, and is roasted for 120-600 min at 900-1300 ℃ in an argon atmosphere, so as to be converted into the boron powder with crystallinity;
(2) adding boron powder with crystallinity into an oxidizing inorganic acid solution, ultrasonically dispersing for 0-30 min at 5-40 ℃ by using an ultrasonic instrument, and reacting for 30-240 min in an oil bath at 60-100 ℃;
(3) and (3) diluting the solution obtained in the step (2), performing centrifugal separation, respectively cleaning with deionized water and ethanol, and drying the obtained powder in an oven at 50-80 ℃ for 4-8 h to obtain the boron hexaoxide.
2. The preparation method according to claim 1, wherein in the step (1), the argon atmosphere is high-purity argon with the purity of more than 99%, the flow rate is 30-100 mL/min, the temperature is programmed, and the temperature rise rate is 2-10 ℃/min.
3. The preparation method according to claim 1, wherein in the step (2), the oxidizing inorganic acid is nitric acid, sulfuric acid or hydrogen peroxide.
4. Use of boron hexaoxide obtained by the preparation method of any one of claims 1 to 3 in hydrogen production by photocatalytic water decomposition.
5. Use according to claim 4, characterized in that it comprises the following steps:
adding boron hexa-oxygen into a photocatalytic reaction system, and then adding 10-200 mg: adding 50-120 mL of aqueous solution of alcohol with volume fraction of 0-50% as a solvent, putting in magnetons, vacuumizing a photocatalytic reaction system by a vacuum pump, carrying out a photocatalytic water hydrogen decomposition experiment by using a xenon lamp as a light source under magnetic stirring, carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system at the same reaction interval, and carrying out quantitative analysis by using gas chromatography to determine the content of a product.
6. The use according to claim 5, wherein the aqueous alcohol solution is one or both of methanol and ethanol.
7. The use according to claim 5, wherein the xenon lamp is provided with a 400 nm cut-off filter and the light source is visible light.
8. Use of boron hexaoxide obtained by the production method according to any one of claims 1 to 3 for photocatalytic reduction of carbon dioxide.
9. Use according to claim 8, characterized in that it comprises the following steps:
adding boron hexa-oxygen into a photocatalytic reaction system, and then adding 10-200 mg: adding 1-3 mL of deionized water, replacing air in the photocatalytic reaction system with carbon dioxide gas for 2-5 times, introducing carbon dioxide to normal pressure, carrying out a photocatalytic reduction carbon dioxide experiment by using a xenon lamp as a light source, carrying out one-time sample measurement on the atmosphere in the photocatalytic reaction system at the same reaction interval, and carrying out quantitative analysis by using gas chromatography to determine the content of the product.
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